Controlling the Reaction Pathways of Mixed NOH Reactants in Plasma-Electrochemical Ammonia Synthesis.

Electrochemical activation of dinitrogen (N) is notoriously challenging, typically yielding very low ammonia (NH) production rates. In this study, we present a continuous flow plasma-electrochemical reactor system for the direct conversion of nitrogen from air into ammonia. In our system, nitrogen molecules are first converted into a mixture of NO species in the plasma reactor, which are then fed into an electrochemical reactor.

Gram-Scale, One-Pot Synthesis of a Cofacial Porphyrin Bridged by Ortho-xylene as a Scaffold for Dinuclear Architectures.

Herein, we report the reaction between four 1,2-dibromoxylenes and two tetra-3-pyridylporphyrins for the formation of a cofacial porphyrin core spanned by dipyridinium xylene moieties. The metal-free organic nanocage (oNC) was synthesized in one twenty-four h step at a gram-scale with a 91.5% yield.

Exploring the Te(II)/Te(IV) Redox Couple of a Tellurorosamine Chromophore: Photophysical, Photochemical, and Electrochemical Studies.

A tellurorosamine dye [] undergoes aerobic photooxidation. Although Te(IV) species have been used in a number of oxidations, key Te(IV)-oxo and Te(IV)-bis(hydroxy) intermediates are challenging to study. Under aerobic irradiation with visible light, (λ = 600 nm) transforms into a Te(IV) species (λ = 669 nm).

Intracranial Efficacy of Atezolizumab, Bevacizumab, Carboplatin, and Paclitaxel in Real-World Patients with Non-Small-Cell Lung Cancer and EGFR or ALK Alterations.

Contrary to Pemetrexed-containing chemo-immunotherapy studies, Atezolizumab, Bevacizumab, Carboplatin, and Paclitaxel (ABCP) treatment has consistently shown clinical benefit in prospective studies in patients with lung cancer and actionable mutations, where intracranial metastases are common. Here, we aimed to describe the real-life population of patients fit to receive ABCP after targeted therapy and quantify its clinical effect in patients with brain metastases. Patients treated in Cheshire and Merseyside between 2019 and 2022 were identified.

Low-Loading Mixed Matrix Materials: Fractal-Like Structure and Peculiarly Enhanced Gas Permeability.

Mixed matrix materials (MMMs) containing metal-organic framework (MOF) nanoparticles are attractive for membrane carbon capture. Particularly, adding <5 mass % MOFs in polymers dramatically increased gas permeability, far surpassing the Maxwell model's prediction. However, no sound mechanisms have been offered to explain this unusual low-loading phenomenon.

Electrocatalytic Production of Hydrogen Peroxide Enabled by Post-Synthetic Modification of a Self-Assembled Porphyrin Cube.

Self-assembled metallacyles and cages formed via coordination chemistry have been used as catalysts to enforce 4H/4e reduction of oxygen to water with an emphasis on attenuating the formation of hydrogen peroxide. That said, the kinetically favored 2H/2e reduction to HO is critically important to industry. In this work we report the synthesis, characterization, and electrochemical benchmarking of a hexa-porphyrin cube which catalyses the electrochemical reduction of molecular oxgyen to hydrogen peroxide.

Investigations of Nanoparticle Suspensions of Prussian Blue and Its Copper Analogue: Amine Functionalization and Electrochemical Studies.

Prussian blue (PB) and its analogues are promising materials for electrochemical energy storage, yet their use in flow-type devices is limited by their lack of redox responsiveness as colloidal suspensions. We have investigated the redox chemistry amine functionalization of PB along with its Cu analogue (CuPBA). No redox response of colloidal PB was observed and suspensions of CuPBA formed films on electrode surfaces with and without applied potentials; the films were redox-active but the material that remained suspended in solution did not participate in redox chemistry.

Altering the solubility of metal-organic polyhedra pendant functionalization of CpZrO(OH) nodes.

The chemistry of zirconium-based metal-organic polyhedra (ZrMOPs) is often limited by their poor solubilities. Despite their attractive features-including high yielding and facile syntheses, predictable topologies, high stability, and tunability-problematic solubilities have caused ZrMOPs to be under-studied and under-applied. Although these cages have been synthesized with a wide variety of carboxylate-based bridging ligands, we explored a new method for ZrMOP functionalization node-modification, which we hypothesized could influence solubility.

The rigidity of self-assembled cofacial porphyrins influences selectivity and kinetics of oxygen reduction electrocatalysis.

We report the electrocatalytic Oxygen Reduction Reaction on a rigid Co(II) porphyrin prism scaffold bridged by Ag(I) ions. The reactivity of this scaffold differs significantly from previous prism catalysts in that its selectivity is similar to that of monomer (∼35% HO) yet it displays sluggish kinetics, with an order of magnitude lower of ∼0.5 M s.

Lowering the Symmetry of Cofacial Porphyrin Prisms for Selective Oxygen Reduction Electrocatalysis.

Cofacial porphyrin catalysts for the Oxygen Reduction Reaction (ORR) formed via coordination-driven self-assembly have so far been limited to designs with fourfold symmetry, where four molecular clips bridge two porphyrin sites. We have synthesized six PyPh (Py = pyridyl, Ph = phenyl) metalloporphyrin prisms (Co, Zn) bridged by molecular clips containing two Rh centers. Four of these structures are lower symmetry, with the PyPh and PyPh prisms containing three and two molecular clips, respectively.

Metal-Organic Polyhedron with Four Fe(III) Centers Producing Enhanced T Magnetic Resonance Imaging Contrast in Tumors.

A metal-organic polyhedron (MOP) with four paramagnetic Fe(III) centers was studied as a magnetic resonance imaging (MRI) probe. The MOP was characterized in solution by using electron paramagnetic resonance (EPR), UV-visible (UV-vis) spectroscopies, Fourier-transform ion cyclotron resonance (FT-ICR) mass spectrometry, and in the solid state with single-crystal X-ray diffraction. Water proton T relaxation properties were examined in solution and showed significant enhancement in the presence of human serum albumin (HSA).

Supramolecular cancer nanotheranostics.

Among the many challenges in medicine, the treatment and cure of cancer remains an outstanding goal given the complexity and diversity of the disease. Nanotheranostics, the integration of therapy and diagnosis in nanoformulations, is the next generation of personalized medicine to meet the challenges in precise cancer diagnosis, rational management and effective therapy, aiming to significantly increase the survival rate and improve the life quality of cancer patients. Different from most conventional platforms with unsatisfactory theranostic capabilities, supramolecular cancer nanotheranostics have unparalleled advantages in early-stage diagnosis and personal therapy, showing promising potential in clinical translations and applications.

Tuning the Reactivity of Cofacial Porphyrin Prisms for Oxygen Reduction Using Modular Building Blocks.

We assembled eight cofacial porphyrin prisms using MTPyP (M = Co(II) or Zn(II), TPyP = 4-tetrapyridylporphyrin) and functionalized ruthenium-based "molecular clips" using coordination-driven self-assembly. Our approach allows for the rapid synthesis of these architectures in isolated yields as high as 98% for the assembly step. Structural and reactivity studies provided a deeper understanding of the role of the building blocks on the oxygen reduction reaction (ORR).

A Self-Assembled Iron(II) Metallacage as a Trap for Per- and Polyfluoroalkyl Substances in Water.

An anionic iron(II) tetrahedral molecular cage (FeMOP) was studied for its ability to interact with various per- and polyfluoroalkyl substances (PFASs) in aqueous media. Liquid chromatography tandem mass spectrometry revealed that longer-chain-length (more than six carbons) perfluorocarboxylic, -sulfonic, and fluorotelomers were removed from solution. In contrast, the steric bulk of -ethyl substituted fluorosulfonamido acetic acid PFASs hindered association with the cage.

MEMS Deformable Mirrors for Space-Based High-Contrast Imaging.

Micro-Electro-Mechanical Systems (MEMS) Deformable Mirrors (DMs) enable precise wavefront control for optical systems. This technology can be used to meet the extreme wavefront control requirements for high contrast imaging of exoplanets with coronagraph instruments. MEMS DM technology is being demonstrated and developed in preparation for future exoplanet high contrast imaging space telescopes, including the Wide Field Infrared Survey Telescope (WFIRST) mission which supported the development of a 2040 actuator MEMS DM.

Understanding the Effects of Coordination and Self-Assembly on an Emissive Phenothiazine.

The local environment surrounding luminophores can significantly influence their photophysical properties. Herein, we report the self-assembly of a highly emissive platinum(II)-based metallacage. In order to accommodate the connectivity of the platinum(II) building block used in the self-assembly process, the luminophore-containing building block adopts a highly twisted geometry relative to its free form, leading to the emergence of an emissive transition with a radiative rate constant an order of magnitude higher than that of the free luminophore.

Fiber-coupled LWIR hyperspectral sensor suite for non-contact component surface temperature measurements.

We report on the development of a robust fiber-coupled long-wavelength infrared (LWIR) hyperspectral sensor suite for accurate and reliable non-contact surface temperature measurements in propulsion systems with limited optical access. We first experimentally investigate various state-of-the-art LWIR optical fibers and identify the ideal fiber for efficient coupling and transmission of LWIR signals. The effects of the fiber material, structure, bending, and thermal heating on LWIR fiber transmission are characterized.

A discrete organoplatinum(II) metallacage as a multimodality theranostic platform for cancer photochemotherapy.

Photodynamic therapy is an effective alternative to traditional treatments due to its minimally invasive nature, negligible systemic toxicity, fewer side effects, and avoidance of drug resistance. However, it is still challenging to design photosensitizers with high singlet oxygen (O) quantum yields (QY) due to severe aggregation of the hydrophobic photosensitizers. Herein, we developed a discrete organoplatinum(II) metallacage using therapeutic cis-(PEt)Pt(OTf) as the building block to improve the O QY, thus achieving synergistic anticancer efficacy.

Tuning the Activity of Heterogeneous Cofacial Cobalt Porphyrins for Oxygen Reduction Electrocatalysis through Self-Assembly.

We report a suite of coordination-driven self-assembled prisms for heterogeneous electrocatalytic oxygen reduction (ORR) differing in the molecular clips linking two porphyrin faces in a cofacial arrangement. ORR activities and selectivities of monomeric CoTPyP along with cofacial prisms Ox-Co, Oxa-Co, and Benzo-Co were probed using cyclic voltammetry and rotating ring-disk techniques. All species were immobilized as heterogeneous catalysts on glassy carbon electrodes using a Nafion ink method.

Highly Emissive Self-Assembled BODIPY-Platinum Supramolecular Triangles.

Light-emitting supramolecular coordination complexes (SCCs) have been widely studied for applications in the chemical and biological sciences. Herein, we report the coordination-driven self-assembly of two highly emissive platinum(II) supramolecular triangles (1 and 2) containing BODIPY-based bridging ligands. The metallacycles exhibit favorable anticancer activities against HeLa cells (IC of 6.